JP2016170269A - Anti-glare film, polarizing plate, and liquid crystal display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anti-glare film that has excellent polarizing plate durability and a good anti-glare property and pencil hardness, and a polarizing plate and a liquid crystal display using the anti-glare film.SOLUTION: There is provided an anti-glare film including an anti-glare layer on a cellulose acylate film, where the cellulose acylate film includes a compound represented by the following general formula (1) and a sugar ester compound; the anti-glare layer has a thickness of 3.0 μm or more and 7.0 μm or less; the anti-glare layer is formed by curing a photocurable composition including at least (a) a curable compound, (b) resin particles, and (c) photopolymerization initiator; the content of the (b) resin particles relative to the solid content in the photocurable composition is 3 mass% or more and 10 mass% or less; the content of the (c) photopolymerization initiator is 1.5 mass% or more and 5 mass% or less. Also provided are a polarizing plate and a liquid crystal display using the anti-glare film.SELECTED DRAWING: None

Description

  The present invention relates to an antiglare film, a polarizing plate, and a liquid crystal display device.

Liquid crystal display devices are increasingly used year by year as space-saving image display devices with low power consumption.
The basic configuration of a liquid crystal display device is one in which polarizing plates are provided on both sides of a liquid crystal cell. The polarizing plate plays a role of allowing only light having a polarization plane in a certain direction to pass through, and the performance of the liquid crystal display device is greatly influenced by the performance of the polarizing plate. The polarizing plate generally has a configuration in which a polarizer made of a polyvinyl alcohol film or the like on which iodine or a dye is adsorbed and oriented, and a protective film (polarizing plate protective film) are bonded to both sides of the polarizer. As a polarizing plate protective film, a film using cellulose acylate typified by cellulose acetate is widely used because it has high transparency and can easily ensure adhesion with polyvinyl alcohol used in a polarizer. .

  In addition, as a protective film provided on the surface of image display devices represented by liquid crystal displays (LCD), plasma display panels (PDP), electroluminescence displays (ELD), etc., it is generally scratch-resistant on cellulose acylate films. In order to prevent a decrease in contrast due to reflection of external light or reflection of an image, a layer provided with an antiglare layer is used. Especially as such a protective film, it arrange | positions at the most visual recognition side of the visual recognition side polarizer.

  In recent years, in addition to indoor applications such as televisions, as the market for outdoor applications such as mobile phones, tablet PCs, and electronic signboards has expanded, the demand for durability of liquid crystal display devices has become stricter. In addition, for the long-term use in harsh environments, suppression of polarization performance deterioration has become a major issue.

Patent Document 1 discloses a cellulose acylate film including a barbituric acid having a specific structure and a sugar ester compound, which has excellent polarizing plate durability, and further includes a hard coat layer provided thereon. Yes.
On the other hand, Patent Document 2 discloses an antiglare film having an antiglare property and a high pencil hardness, and having an antiglare layer provided on a cellulose acylate film containing barbituric acid having a specific structure. Has been.

JP 2014-210905 A JP 2014-199424 A

In the market, there has been a demand for an optical film having high pencil hardness, antiglare properties, and high polarizing plate durability.
Accordingly, an object of the present invention is to provide an antiglare film having excellent polarizing plate durability and antiglare properties and good pencil hardness, and a polarizing plate and a liquid crystal display device using the same.

  The above problem can be solved by the following means.

Ｒ^１３はアルキル基、アルケニル基又はアリール基を表し、Ｒ^１１及びＲ^１２はそれぞれ独立して水素原子、アルキル基、アルケニル基、アリール基又はヘテロアリール基を表す。Ｒ^１１、Ｒ^１２、及びＲ^１３はそれぞれ独立に置換基を有していてもよい。ただし、Ｒ^１１、Ｒ^１２、及びＲ^１３のいずれか少なくとも１つは芳香環を含む。
［２］
上記防眩層の厚みが３．０μｍ以上５．０μｍ以下である［１］に記載の防眩フィルム。
［３］
上記ｂ）樹脂粒子の含有量が上記光硬化性組成物中の固形分に対して３質量％以上８．５質量％以下である［１］又は［２］に記載の防眩フィルム。
［４］
上記ｃ）光重合開始剤の含有量が上記光硬化性組成物中の固形分に対して１．５質量％以上３質量％以下である［１］〜［３］のいずれかに記載の防眩フィルム。
［５］
上記一般式（１）で表される化合物が、下記一般式（２−ａ）で表される化合物である［１］〜［４］のいずれかに記載の防眩フィルム。

Ｌ^１〜Ｌ^３は、各々独立に、単結合又はアルキレン基を表す。Ａｒ^１〜Ａｒ^３は各々独立に、炭素数６〜２０のアリール基を表す。
［６］
［１］〜［５］のいずれかに記載の防眩フィルムと偏光子とを少なくとも有する偏光板。
［７］
［６］に記載の偏光板と液晶セルとを少なくとも有する液晶表示装置。 [1]
An antiglare film having an antiglare layer on a cellulose acylate film,
The cellulose acylate film contains a compound represented by the following general formula (1) and a sugar ester compound,
The antiglare layer has a thickness of 3.0 μm or more and 7.0 μm or less,
The antiglare layer is formed by curing a photocurable composition containing at least a) a curable compound, b) resin particles, and c) a photopolymerization initiator,
The content of the b) resin particles with respect to the solid content in the photocurable composition is 3% by mass or more and 10% by mass or less, and the content of the c) photopolymerization initiator is 1.5% by mass or more and 5% by mass. % Or less antiglare film.

R ¹³ represents an alkyl group, an alkenyl group or an aryl group, and R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heteroaryl group. R ¹¹ , R ¹² , and R ¹³ may each independently have a substituent. However, at least one of R ¹¹ , R ¹² , and R ¹³ includes an aromatic ring.
[2]
The antiglare film according to [1], wherein the antiglare layer has a thickness of 3.0 μm or more and 5.0 μm or less.
[3]
The antiglare film according to [1] or [2], wherein the content of the b) resin particles is 3% by mass or more and 8.5% by mass or less with respect to the solid content in the photocurable composition.
[4]
The content of the said c) photoinitiator is 1.5 mass% or more and 3 mass% or less with respect to solid content in the said photocurable composition, The prevention in any one of [1]-[3] Dazzle film.
[5]
The antiglare film according to any one of [1] to [4], wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2-a).

L ^{1 to} L ³ each independently represents a single bond or an alkylene group. Ar ^{1 to} Ar ³ each independently represents an aryl group having 6 to 20 carbon atoms.
[6]
A polarizing plate having at least the antiglare film according to any one of [1] to [5] and a polarizer.
[7]
A liquid crystal display device having at least the polarizing plate according to [6] and a liquid crystal cell.

  According to the present invention, it is possible to provide an antiglare film having excellent polarizing plate durability, antiglare properties, and good pencil hardness. In addition, a polarizing plate and a liquid crystal display device using the antiglare film can be provided.

It is the schematic which shows an example which showed the internal structure of the liquid crystal display device typically. It is the schematic which shows an example when the cellulose acylate film of a three-layer structure is poured by simultaneous co-casting using a co-casting die.

Hereinafter, the present invention will be described in detail.
The antiglare film of the present invention is an antiglare film having an antiglare layer on a cellulose acylate film, and the cellulose acylate film contains a compound represented by the following general formula (1) and a sugar ester compound, The antiglare layer has a thickness of 3.0 μm or more and 7.0 μm or less, and the antiglare layer cures a photocurable composition containing at least a) a curable compound, b) resin particles, and c) a photopolymerization initiator. And b) the content of the resin particles with respect to the solid content in the photocurable composition is 3% by mass or more and 10% by mass or less, and c) the content of the photopolymerization initiator is 1.5% by mass or more and 5% or less. It is an anti-glare film that is not more than mass%.

R ¹³ represents an alkyl group, an alkenyl group or an aryl group, and R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heteroaryl group. R ¹¹ , R ¹² , and R ¹³ may each independently have a substituent. However, at least one of R ¹¹ , R ¹² , and R ¹³ includes an aromatic ring.

When the present inventors imparted an antiglare layer on the cellulose acylate film, the content of the resin particles and photopolymerization initiator contained in the composition for forming the antiglare layer is reduced. The knowledge that the polarizing plate durability is improved was obtained. Although the mechanism of this action is unknown, there is a possibility that the resin particles of the antiglare layer and the photopolymerization initiator interact with the components constituting the polarizer.
The antiglare film of the present invention is to reduce the resin particle content in the antiglare layer, the photopolymerization initiator content, and the film thickness of the antiglare layer in a range that does not impair the antiglare property and film hardness. Good polarizing plate durability, anti-glare properties, and film hardness are achieved.

<< Anti-Glare Film >>
[Cellulose acylate film]
The cellulose acylate film used for the antiglare film of the present invention (hereinafter also referred to as the cellulose acylate film of the present invention) contains a compound represented by the following general formula (1) and a sugar ester compound. The compound represented by the general formula (1) can contribute as a polarizer durability improver.

<Compound represented by the general formula (1)>

R ₁₃ represents an alkyl group, an alkenyl group or an aryl group, and R ₁₁ and R ₁₂ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heteroaryl group. R ₁₁ , R ₁₂ , and R ₁₃ may each independently have a substituent. However, at least one of R ₁₁ , R ₁₂ , and R ₁₃ includes an aromatic ring.

R ₁₃ is preferably an alkyl group having 1 to 20 carbon atoms (including a cycloalkyl group), an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and an alkyl group having 1 to 12 carbon atoms. (Including a cycloalkyl group), more preferably an alkenyl group having 2 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 12 carbon atoms (including a cycloalkyl group), carbon More preferably, it is an alkenyl group having 2 to 10 carbon atoms or an aryl group having 6 to 18 carbon atoms, an alkyl group having 1 to 8 carbon atoms (including a cycloalkyl group), an alkenyl group having 2 to 5 carbon atoms or carbon. An aryl group having 6 to 12 carbon atoms is particularly preferable, and an alkyl group having 1 to 6 carbon atoms (including a cycloalkyl group) or an aryl group having 6 to 12 carbon atoms is most preferable. Yes.
Among these, a methyl group, an ethyl group, a propyl group, a cyclohexyl group, a phenyl group or a naphthyl group is more preferable, and a methyl group, a cyclohexyl group or a phenyl group is most preferable.

R ₁₁ and R ₁₂ are each independently an alkyl group having 1 to 20 carbon atoms (including a cycloalkyl group), an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkyl group having 6 to 20 carbon atoms. It is preferably a heteroaryl group, more preferably an alkyl group having 1 to 12 carbon atoms (including a cycloalkyl group), an alkenyl group having 2 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and 1 carbon atom. It is more preferable that they are a C12 alkyl group (a cycloalkyl group is also included), a C2-C10 alkenyl group, or a C6-C18 aryl group, and a C1-C8 alkyl group (cycloalkyl group). In particular, an alkenyl group having 2 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms, and an alkyl group having 1 to 6 carbon atoms (including a cycloalkyl group). ), Or most preferably an aryl group having 6 to 12 carbon atoms.
Among these, a methyl group, an ethyl group, a propyl group, a cyclohexyl group, a phenyl group, or a naphthyl group is most preferable, and a methyl group, an ethyl group, a cyclohexyl group, or a phenyl group is particularly preferable.

The substituent that R ₁₃ may have is not particularly limited as long as it does not contradict the gist of the present invention, but is preferably a halogen atom, an alkyl group, or an aryl group, preferably a halogen atom, a carbon number of 1 to It is more preferably an alkyl group having 6 or an aryl group having 6 to 12 carbon atoms, and particularly preferably a chlorine atom, a methyl group, or a phenyl group.

The substituent that R ₁₁ and R ₁₂ may have is not particularly limited as long as it does not contradict the gist of the present invention, but is preferably an aryl group having 6 to 12 carbon atoms, and is a phenyl group. Is more preferable.

  As the compound represented by the general formula (1), a compound represented by the following general formula (2-a) can be preferably used. The compound represented by the general formula (2-a) is preferable from the viewpoint of polarizing plate durability and suppression of volatilization during film formation.

In the general formula (2-a), L ^{1 to} L ³ each independently represents a single bond or an alkylene group. Ar ^{1 to} Ar ³ each independently represents an aryl group having 6 to 20 carbon atoms.

In the general formula (2-a), L ^{1 to} L ³ each independently represents a single bond or an alkylene group. L ^{1 to} L ³ are more preferably a single bond or an alkylene group having 1 to 6 carbon atoms, more preferably a single bond, a methylene group or an ethylene group, and particularly preferably a single bond or a methylene group. preferable. The divalent linking group may have a substituent, and the substituent is synonymous with the substituent that Ar ¹ , Ar ² , and Ar ³ described later may have.

In the general formula (2-a), Ar ^{1 to} Ar ³ each independently represents an aryl group having 6 to 20 carbon atoms, preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. Ar ¹ to Ar ³ may have a substituent, the substituent has the same meaning as the substituents may have the ^Ar 1, Ar ^2, and Ar ³ described later. Ar ^{1 to} Ar ³ do not have a substituent, or when it has a substituent, the substituent preferably has no ring structure.

Ar ¹ , Ar ² , and Ar ³ may have a substituent. The substituent is not particularly limited, and may be an alkyl group (preferably having 1 to 10 carbon atoms such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1 -Carboxymethyl, etc.), alkenyl groups (preferably having 2 to 20 carbon atoms, such as vinyl, allyl, oleyl, etc.), alkynyl groups (preferably having 2 to 20 carbon atoms, such as ethynyl, butadiynyl, phenylethynyl, etc.) A cycloalkyl group (preferably having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.), an aryl group (preferably having 6 to 26 carbon atoms, such as phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, etc.), hete A cyclic group (preferably a heterocyclic group having 0 to 20 carbon atoms, wherein the ring-constituting hetero atom is preferably an oxygen atom, a nitrogen atom or a sulfur atom, even if it is a 5- or 6-membered ring and condensed with a benzene ring or a heterocyclic ring. The ring may be a saturated ring, an unsaturated ring, or an aromatic ring. For example, 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl, etc.), an alkoxy group ( Preferably having 1 to 20 carbon atoms, for example, methoxy, ethoxy, isopropyloxy, benzyloxy, etc.), aryloxy groups (preferably having 6 to 26 carbon atoms, such as phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy etc.),

An alkylthio group (preferably having 1 to 20 carbon atoms, such as methylthio, ethylthio, isopropylthio, benzylthio, etc.), an arylthio group (preferably having 6 to 26 carbon atoms, such as phenylthio, 1-naphthylthio, 3-methylphenylthio, etc. , 4-methoxyphenylthio, etc.), acyl groups (including alkylcarbonyl groups, alkenylcarbonyl groups, arylcarbonyl groups, and heterocyclic carbonyl groups, preferably having 20 or less carbon atoms, such as acetyl, pivaloyl, acryloyl, metachloroyl, benzoyl , Nicotinoyl, etc.), aryloylalkyl group, alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.), aryloxycarbonyl group (preferably having 7 to 7 carbon atoms). 0, for example, phenyloxycarbonyl, naphthyloxycarbonyl, etc.), an amino group (including amino group, alkylamino group, arylamino group, heterocyclic amino group, preferably 0-20 carbon atoms, for example, amino, N , N-dimethylamino, N, N-diethylamino, N-ethylamino, anilino, 1-pyrrolidinyl, piperidino, morphonyl, etc.), sulfonamide group (preferably having 0 to 20 carbon atoms, for example, N, N-dimethylsulfone, for example) Amide, N-phenylsulfonamide and the like), sulfamoyl group (preferably having 0 to 20 carbon atoms, for example, N, N-dimethylsulfamoyl, N-phenylsulfamoyl etc.), acyloxy group (preferably having 1 carbon atom) -20, for example, acetyloxy, benzoyloxy, etc.), carbamoyl group (preferably Has 1 to 20 carbon atoms, for example, N, N-dimethylcarbamoyl, N-phenylcarbamoyl, etc.), acylamino group (preferably 1 to 20 carbon atoms, for example, acetylamino, acryloylamino, benzoylamino, nicotinamide, etc. ), Cyano group, hydroxyl group, mercapto group or halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.).

The substituent that Ar ¹ , Ar ² , and Ar ³ may have may further have the substituent.

Here, among the above substituents that each of Ar ¹ , Ar ² , and Ar ³ may have, an alkyl group, an aryl group, an alkoxy group, and an acyl group are preferable.

The molecular weight of the compound represented by the general formula (1) or (2-a) is preferably 250 to 1200, and more preferably 300 to 800.
If the molecular weight is 250 or more, volatilization from the film is suppressed, and if it is 1200 or less, the compatibility with the cellulose acylate is excellent, and thus the transparency of the film is good.

  Specific examples of the compound represented by the general formula (1) or (2-a) are shown below, but the present invention is not limited thereto. In the following exemplary compounds, Me represents a methyl group.

It is known that the compound represented by the general formula (1) can be synthesized using a synthesis method of barbituric acid in which a urea derivative and a malonic acid derivative are condensed. For barbituric acid having two substituents on the nitrogen atom, heat N, N 'disubstituted urea and malonic acid chloride or a combination of malonic acid and an activator such as acetic anhydride. For example, Journal of the American Chemical Society, Vol. 61, p. 1015 (1939), Journal of Medicinal.
Chemistry, 54, 2409 (2011), Tetrahedron
Letters, 40, 8029 (1999), International Publication No. 2007/150011 pamphlet and the like can be preferably used.
In addition, the malonic acid used for the condensation may be unsubstituted or substituted, and if malonic acid having a substituent corresponding to R ¹³ is used, a barbituric acid is constructed to construct the general formula (1) Can be synthesized. Further, when the unsubstituted malonic acid and the urea derivative are condensed, a 5-position unsubstituted barbituric acid is obtained. By modifying this, the compound represented by the general formula (1) may be synthesized. .

As a method for modifying the 5-position, an addition reaction such as a nucleophilic substitution reaction with an alkyl halide or the like or a Michael addition reaction can be used. In addition, a method in which an alkylidene or arylidene compound is produced by dehydration condensation with an aldehyde or a ketone and then a double bond is reduced can be preferably used. For example, a reduction method using zinc is described in Tetrahedron Letters, 44, 2203 (2003), and a reduction method using catalytic reduction is Tetrahedron Letters, 42, 4103 (2001) or Journal of the American Chemical, 119, 12849 (1997), reduction methods using NaBH4 are described in Tetrahedron Letters, 28, 4173 (1987), respectively. These are all synthetic methods that can be preferably used in the case of having an aralkyl group at the 5-position or a cycloalkyl group.
In addition, the synthesis | combining method of the compound represented by General formula (1) used for this invention is not limited above.

The content of the compound represented by the general formula (1) in the cellulose acylate film is not particularly limited, but is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of cellulose acylate. It is more preferably 2 to 15 parts by mass, and particularly preferably 0.3 to 10 parts by mass.
By making the addition amount of the compound represented by the general formula (1) in the above range, the durability of the polarizing plate is effectively improved and the occurrence of haze is suppressed.

<Sugar ester compound>
The cellulose acylate film used in the present invention contains a sugar ester compound. By including a sugar ester compound, a cellulose acylate film excellent in humidity stability and polarizing plate durability can be obtained.
The sugar ester compound is preferably a monosaccharide or a carbohydrate derivative containing 2 to 10 monosaccharide units. The sugar ester compound is also referred to as a carbohydrate derivative plasticizer in the following.

  The monosaccharide or polysaccharide preferably constituting the carbohydrate derivative plasticizer has a part or all of the substitutable groups in the molecule (for example, hydroxy group, carboxyl group, amino group, mercapto group, etc.) substituted with substituents. . Examples of the substituent that the carbohydrate derivative plasticizer may have include an alkyl group, an aryl group, and an acyl group. Details will be described later. Moreover, an ether structure formed by substitution with an alcohol, an ester structure formed by substitution of a hydroxy group with an acyl group, an amide structure or an imide structure formed by substitution with an amino group, and the like can be given.

  Carbohydrates containing monosaccharides or 2-10 monosaccharide units are erythrose, threose, ribose, arabinose, xylose, lyxose, allose, altrose, glucose, fructose, mannose, gulose, idose, galactose, talose, trehalose, iso Trehalose, neotrehalose, trehalosamine, cobibiose, nigerose, maltose, maltitol, isomaltose, sophorose, laminaribiose, cellobiose, gentiobiose, lactose, lactosamine, lactitol, lactulose, melibiose, primeverose, lutinose, silabiose, sucrose , Vicyanose, cellotriose, cacotriose, gentianose, isomaltotriose, isopano , Maltotriose, manninotriose, melezitose, panose, planteose, raffinose, solatriose, umbelliferose, lycotetraose, maltotetraose, stachyose, baltopentaose, velval course, maltohexaose, α- Cyclodextrin, β-cyclodextrin, γ-cyclodextrin, δ-cyclodextrin, xylitol or sorbitol is preferred.

  Preferably, ribose, arabinose, xylose, lyxose, glucose, fructose, mannose, galactose, trehalose, maltose, cellobiose, lactose, sucrose, sucralose, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, δ-cyclodextrin Xylitol, sorbitol, more preferably arabinose, xylose, glucose, fructose, mannose, galactose, maltose, cellobiose, sucrose, β-cyclodextrin, or γ-cyclodextrin, particularly preferably xylose, glucose, Fructose, mannose, galactose, maltose, cellobiose, sucrose, xylitol, or sorbitol

The substituent of the carbohydrate derivative plasticizer is an alkyl group (preferably an alkyl group having 1 to 22 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms, such as methyl, ethyl, Propyl, hydroxyethyl, hydroxypropyl, 2-cyanoethyl, benzyl group, etc.), aryl groups (preferably 6-24 carbon atoms, more preferably 6-18, particularly preferably 6-12 aryl groups such as phenyl, naphthyl, etc. ), An acyl group (including an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, preferably an acyl group having 1 to 22 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms. Acetyl, propionyl, butyryl, pentanoyl, hexanoyl, octanoyl, benzoyl, toluyl Phthalyl, such as Nafutoru) is preferred. Further, as a preferred structure formed by substitution with an amino group, an amide structure (preferably an amide having 1 to 22 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as formamide, acetamide, etc. Etc.) or an imide structure (preferably an imide having 4 to 22 carbon atoms, more preferably 4 to 12 carbon atoms, and particularly preferably 4 to 8 carbon atoms, such as succinimide and phthalimide).
The substituent that the carbohydrate derivative plasticizer has is preferably at least one selected from an alkyl group, an aryl group, and an acyl group, and more preferably an acyl group.

Preferable examples of the carbohydrate derivative plasticizer include the following, but the present invention is not limited thereto.
Xylose tetraacetate, glucose pentaacetate, fructose pentaacetate, mannose pentaacetate, galactose pentaacetate, maltose octaacetate, cellobiose octaacetate, sucrose octaacetate, xylitol pentaacetate, sorbitol hexaacetate, xylose tetrapropionate, glucose pentapropioate , Fructose pentapropionate, mannose pentapropionate, galactose pentapropionate, maltose octapropionate, cellobiose octapropionate, sucrose octapropionate, xylitol pentapropionate, sorbitol hexapropionate, Xylose tetrabutyrate, glucose pentab Rate, fructose pentabylate, mannose pentabylate, galactose pentabylate, maltose octabutyrate, cellobiose octabutyrate, sucrose octabutyrate, xylitol pentabylate, sorbitol hexabutyrate, xylose tetrabenzoate, glucose pentabenzoate, At least one selected from fructose pentabenzoate, mannose pentabenzoate, galactose pentabenzoate, maltose octabenzoate, cellobiose octabenzoate, sucrose octabenzoate, xylitol pentabenzoate, and sorbitol hexabenzoate.

  More preferably, xylose tetraacetate, glucose pentaacetate, fructose pentaacetate, mannose pentaacetate, galactose pentaacetate, maltose octaacetate, cellobiose octaacetate, sucrose octaacetate, xylitol pentaacetate, sorbitol hexaacetate, xylose tetrapropionate, Glucose pentapropionate, fructose pentapropionate, mannose pentapropionate, galactose pentapropionate, maltose octapropionate, cellobiose octapropionate, sucrose octapropionate, xylitol pentapropionate, sorbitol hexa Propionate, xylose tetrabenzoate, Le courses pentabenzoate, fructose pentabenzoate, mannose pentabenzoate, galactose pentabenzoate, maltose octabenzoate, cellobiose octabenzoate, sucrose octabenzoate, at least one selected from xylitol pentabenzoate and sorbitol hexa benzoate.

More preferably, maltose octaacetate, cellobiose octaacetate, sucrose octaacetate, xylose tetrapropionate, glucose pentapropionate, fructose pentapropionate, mannose pentapropionate, galactose pentapropionate, maltose octapropionate Nate, cellobiose octapropionate, sucrose octapropionate, xylose tetrabenzoate, glucose pentabenzoate, fructose pentabenzoate, mannose pentabenzoate, galactose pentabenzoate, maltose octabenzoate, cellobiose octabenzoate, sucrose octabenzoate, xylitol pentabenzoate, And sorbitol hex At least one selected from the group consisting of benzoate.
The carbohydrate derivative plasticizer preferably has a pyranose structure or a furanose structure.

As the sugar ester compound used in the present invention, the following compounds are also preferred. However, the present invention is not limited to these.
In the following structural formulas, R each independently represents an arbitrary substituent, and a plurality of R may be the same or different.
In the following Tables 1 to 4, those which are hydroxy groups in one molecule (R are both hydrogen atoms) are acylated with two types of acylating agents, and are introduced with these two types of acylating agents. One of the Rs is shown as “Substituent 1”, and the other R is shown as “Substituent 2”, and the degree of substitution represents the number of all hydroxy groups in one molecule.

  As the sugar ester compound, commercially available products such as those manufactured by Tokyo Kasei Co., Ltd. and Aldrich can be obtained, and commercially available carbohydrates can be obtained by known esterification reactions (for example, described in JP-A-8-245678). Method).

As for content of the sugar ester compound in the cellulose acylate film of this invention, 1-20 mass parts is preferable with respect to 100 mass parts of cellulose acylates. By setting the content of the sugar ester compound to 1 part by mass or more with respect to 100 parts by mass of cellulose acylate, the effect of improving the durability of the polarizer can be easily obtained, and by controlling the content to 20 parts by mass or less, bleeding out is also suppressed. it can. The more preferable content of the sugar ester compound in the cellulose acylate film is 2 to 15 parts by mass, particularly preferably 5 to 15 parts by mass with respect to 100 parts by mass of the cellulose acylate.
Two or more kinds of these sugar ester compounds may be added. Also when adding 2 or more types, the specific example and preferable range of addition amount are the same as the above.

<Cellulose acylate>
Hereinafter, the cellulose acylate that can be used in the present invention will be described in detail. In the present invention, cellulose acylate is used as the main component of the film. Here, in the present specification, the “main component” refers to a component having a highest mass fraction in an embodiment in which there is one component as a raw material and in an embodiment having two or more components. One type of cellulose acylate may be used, or two or more types may be used. The acyl substituent of the cellulose acylate may be, for example, a cellulose acylate composed of an acetyl group alone, or a cellulose acylate having a plurality of different acyl substituents, or a mixture of different cellulose acylates. May be.

  Cellulose acylate raw material cellulose used in the present invention includes cotton linter and wood pulp (hardwood pulp, conifer pulp), and any cellulose acylate obtained from any raw material cellulose can be used and mixed in some cases. May be used. Detailed descriptions of these raw material celluloses can be found in, for example, Marusawa and Uda, “Plastic Materials Course (17) Fibrous Resin”, Nikkan Kogyo Shimbun (published in 1970), and Japan Institute of Invention and Publications. The cellulose described in 2001-1745 (pages 7-8) can be used.

  In the present invention, the acyl group of cellulose acylate may be only one type, or two or more types of acyl groups may be used. The cellulose acylate used in the present invention preferably has an acyl group having 2 to 4 carbon atoms as a substituent. When two or more kinds of acyl groups are used, one of them is preferably an acetyl group, and the other acyl group having 2 to 4 carbon atoms is preferably a propionyl group or a butyryl group. These cellulose acylates can produce a solution having a preferable solubility, and in particular, a non-chlorine organic solvent can be used to produce a good solution. Further, a solution having a low viscosity and good filterability can be produced.

First, the cellulose acylate preferably used in the present invention will be described in detail.
Glucose units having a β-1,4 bond constituting cellulose have free hydroxy groups at the 2nd, 3rd and 6th positions. Cellulose acylate is a polymer obtained by acylating part or all of these hydroxy groups with an acyl group.
The degree of acyl substitution indicates the degree of acylation of the hydroxy group of cellulose located at the 2-position, 3-position and 6-position, and all the 2-position, 3-position and 6-position hydroxy groups of all glucose units are When acylated, the total acyl substitution degree is 3. For example, when all the glucose units are all acylated in all glucose units, the total acyl substitution degree is 1. Similarly, the total acyl substitution degree is 1 when all of either the 6-position or the 2-position are acylated in each glucose unit in all hydroxy groups of all glucose.
That is, the degree of acylation is indicated by 3 when all hydroxy groups in the glucose molecule are all acylated.
For details of the method for measuring the degree of acyl substitution, see Tezuka et al., Carbohydrate. Res. , 273, 83-91 (1995) and the method specified in ASTM-D817-96.

  The total acyl substitution degree (A) of the cellulose acylate used in the present invention is preferably 1.5 or more and 3 or less (1.5 ≦ A ≦ 3.0), more preferably 2.0 to 2.97, 2 It is more preferably from 0.5 to less than 2.97, particularly preferably from 2.70 to 2.95.

In the cellulose acetate using only acetyl groups as the acyl groups of cellulose acylate, the total acetyl substitution degree (B) is preferably 2.0 or more and 3.0 or less (2.0 ≦ B ≦ 3.0). 2.0 to 2.97, more preferably 2.5 or more and less than 2.97, particularly preferably 2.55 or more and less than 2.97, particularly preferably 2.60 to 2.96. Most preferred is 70-2.95.
The compound represented by the general formula (1) of the present invention is particularly effective for cellulose acylate having a total acetyl substitution degree (B) exceeding 2.50.

  The acyl group having 2 or more carbon atoms of the cellulose acylate used in the present invention may be an aliphatic acyl group or an aromatic acyl group, and is not particularly limited. They are, for example, alkyl carbonyl esters, alkenyl carbonyl esters, aromatic carbonyl esters, or aromatic alkyl carbonyl esters (aralkyl carbonyl esters) of cellulose, which may have a substituent. The acyl group having 2 or more carbon atoms is acetyl, propionyl, butanoyl, pentanoyl, heptanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, isobutanoyl, tert-butanoyl, cyclohexanecarbonyl Oleoyl, benzoyl, naphthylcarbonyl, or cinnamoyl. Among these, acetyl, propionyl, butanoyl, dodecanoyl, octadecanoyl, tert-butanoyl, oleoyl, benzoyl, naphthylcarbonyl, or cinnamoyl is more preferable, and more preferably 2 carbon atoms such as acetyl, propionyl, or butanoyl. ~ 4 acyl groups, more preferably acetyl (i.e., when the cellulose acylate is cellulose acetate).

  In the acylation of cellulose, when an acid anhydride or acid chloride is used as an acylating agent, an organic carboxylic acid solvent or a halogen solvent (for example, acetic acid or methylene chloride) is preferably used as the organic solvent as a reaction solvent.

As the catalyst, when the acylating agent is an acid anhydride, a protic catalyst such as sulfuric acid is preferably used, and when the acylating agent is an acid chloride (for example, CH ₃ CH ₂ COCl), Basic compounds are used.

  The most common industrial synthesis method for cellulose mixed fatty acid esters is a fatty acid corresponding to an acyl group such as an acetyl group (for example, acetic acid corresponding to an acetyl group, propionic acid corresponding to a propionyl group, and a good acid corresponding to a pentanoyl group. This is a method of acylating cellulose using a mixed organic acid component containing a herbic acid or the like) or an acid anhydride of a fatty acid.

  Cellulose acylate can be synthesized, for example, by the method described in JP-A-10-45804.

  From the viewpoint of moisture permeability, the cellulose acylate film of the present invention preferably contains 5 to 99% by mass of cellulose acylate in the total solid content, more preferably 20 to 99% by mass, and more preferably 50 to 95% by mass. It is particularly preferred.

<Other additives>
In the cellulose acylate film of the present invention, a retardation adjusting agent (retardation developing agent and retardation reducing agent), other plasticizers (polycondensation ester compound (polymer), polyhydric alcohol polyhydric ester, phthalic acid) Esters, phosphate esters, etc.), UV absorbers, antioxidants, matting agents, and other additives can be added.
Specific examples of each additive include the additives described in JP 2014-210905 A, paragraph numbers [0066] to [0216], and the like.

(Radical scavenger)
The polarizing plate protective film preferably contains a radical scavenger. As the radical scavenger, HALSs and reductones are preferably used.
The HALS is particularly preferably a compound having a 2,2,6,6-tetramethyl-piperidine ring, and the 1-position of piperidine is a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, an oxy radical group (-O. ), An acyloxy group or an acyl group is preferred, and the 4-position is more preferably a hydrogen atom, a hydroxy group, an acyloxy group, an amino group which may have a substituent, an alkoxy group or an aryloxy group. Those having 2 to 5, 2,2,6,6-tetramethyl-piperidine rings in the molecule are also preferred.
Such compounds include, for example, Sunlizer HA-622 (trade name, manufactured by Sort Co., Ltd.), CHIMASSORB 2020FDL, TINUVIN 770DF, TINUVIN 152, TINUVIN 123, FLAMESTAB NOR 116 FF -Specialty Chemicals Co., Ltd.)], Siasorb UV-3346, Siasorb UV-3529 (trade names, both manufactured by Sun Chemical Co., Ltd.).

Examples of reductones include compounds exemplified in paragraph Nos. 0014 to 0034 of JP-A No. 6-27599, compounds exemplified in paragraph Nos. 0012 to 0020 of JP-A No. 6-110163, and paragraphs of JP-A No. 8-114899. Nos. 0022 to 0031 may include exemplified compounds.
In addition, oil-solubilized derivatives of ascorbic acid and erythorbic acid can be preferably used, and stearic acid L-ascorbyl ester, tetraisopalmitic acid L-ascorbyl ester, palmitic acid L-ascorbyl ester, palmitic acid erythorbyl ester, tetraisopalmitin And acid erythorbyl ester. Among them, those having an ascorbic acid skeleton are preferable, and myristic acid ester, palmitic acid ester, and stearic acid ester of L-ascorbic acid are particularly preferable.
Content of the radical scavenger in a polarizing plate protective film is 0.001-2.0 mass parts with respect to 100 mass parts of resin which comprises a polarizing plate protective film, More preferably, 0.01-1 0.0 part by mass.

(Deterioration inhibitor)
A deterioration preventing agent (eg, antioxidant, peroxide decomposer, radical inhibitor, metal deactivator, acid scavenger, amine) may be added to the polarizing plate protective film. Further, an ultraviolet absorber is one of deterioration preventing agents. These deterioration inhibitors and the like are disclosed in JP-A-60-235852, JP-A-3-199201, JP-A-51907073, JP-A-5-194789, JP-A-5-271471, JP-A-6-107854, JP-A-6-107854. 118233, 6-148430, 7-11056, 7-11055, 7-11056, 8-29619, 8-239509, JP-A-2000-204173, JP-A-2006 There are descriptions in each publication of No. 251746.

The radical scavengers described above also exhibit an anti-degradation action, but amines are also known as anti-degradation agents. For example, compounds described in paragraph Nos. 0009 to 0080 of JP-A-5-194789, and tri-n-octyl Examples thereof include aliphatic amines such as amine, triisooctylamine, tris (2-ethylhexyl) amine, and N, N-dimethyldodecylamine.
It is also preferable to use polyvalent amines having two or more amino groups. As the polyvalent amine, those having two or more primary or secondary amino groups are preferable. Examples of the compound having two or more amino groups include nitrogen-containing heterocyclic compounds (compounds having a pyrazolidine ring, piperazine ring, etc.), polyamine compounds (chain or cyclic polyamines such as diethylenetriamine, tetraethylenepentamine, Based on N, N′-bis (aminoethyl) -1,3-propanediamine, N, N, N ′, N ″, N ″ -pentakis (2-hydroxypropyl) diethylenetriamine, polyethyleneimine, modified polyethyleneimine, cyclam And the like).
The content of the deterioration preventing agent in the polarizing plate protective film is preferably 1 ppm to 10%, more preferably 1 ppm to 5.0%, and even more preferably 10 ppm to 1.0% on a mass basis.

(UV absorber)
There is no restriction | limiting in particular about the ultraviolet absorber which can be used for this invention, All the ultraviolet absorbers conventionally used for the cellulose acylate can be used. As said ultraviolet absorber, the compound as described in Unexamined-Japanese-Patent No. 2006-184874 can be mentioned. Polymer ultraviolet absorbers can also be preferably used. In particular, polymer type ultraviolet absorbers described in JP-A-6-148430 are preferably used. The amount of the UV absorber used is not uniform depending on the type of UV absorber, usage conditions, etc., but the UV absorber is contained in a proportion of 1 to 3% by mass with respect to the cellulose acylate as the main component. More preferably.
Examples include ultraviolet absorbers having the following structure, but the ultraviolet absorbers to be added are not limited to these.

(Matting agent)
A matting agent may be added to the cellulose acylate film from the viewpoint of film slipperiness and stable production. The matting agent may be an inorganic compound matting agent or an organic compound matting agent.
The inorganic compound matting agent is an inorganic compound containing silicon (for example, silicon dioxide, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, etc.), titanium oxide, zinc oxide, aluminum oxide, barium oxide. , Zirconium oxide, strontium oxide, antimony oxide, tin oxide, tin / antimony oxide, calcium carbonate, talc, clay, calcined kaolin and calcium phosphate, and more preferably from silicon-containing inorganic compound and zirconium oxide Although it is at least one selected, it is particularly preferable to use silicon dioxide from the viewpoint of further reducing the turbidity of the cellulose acylate film.

As the fine particles of silicon dioxide, commercially available products having a trade name such as Aerosil R972, R974, R812, 200, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.) can be used. As the fine particles of zirconium oxide, for example, those commercially available under trade names such as Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) can be used.
The matting agent of the organic compound is not particularly limited, but at least one polymer selected from silicone resins, fluororesins and acrylic resins is preferable, and among them, silicone resins are preferable. Among the silicone resins, those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, Tospearl 105, Tospearl 108, Tospearl 120, Tospearl 145, Tospearl 3120 and Tospearl 240 (manufactured by Toshiba Silicone Co., Ltd.) A commercial product having a trade name can be used.

The timing for adding these matting agents to the cellulose acylate film is not particularly limited as long as it is added at the time of film formation. For example, an additive may be contained at the stage of mixing cellulose acylate and a solvent, or an additive may be added after preparing a mixed solution with cellulose acylate and a solvent.
Further, it may be added and mixed immediately before casting the dope, and the mixing is preferably carried out by installing a screw-type kneading on-line. Specifically, it is preferable to use a static mixer such as an in-line mixer. Further, as the in-line mixer, for example, a static mixer SWJ (Toray static type in-pipe mixer Hi-Mixer) (manufactured by Toray Engineering) is preferable.

  As for in-line addition, the method described in JP-A-2003-053752 can be used in order to eliminate density unevenness, particle aggregation, and the like. Furthermore, the method described in JP-A-2003-014933 may be used in order to obtain a retardation film with little additive bleed-out, no delamination phenomenon between layers, and excellent slipperiness and excellent transparency. it can.

  The content of the matting agent in the cellulose acylate film is particularly preferably 0.05 to 1.0% by mass. By setting such a value, the haze of the cellulose acylate film does not increase, and when actually used in a liquid crystal display device, it contributes to suppression of inconveniences such as a decrease in contrast and generation of bright spots. Further, the above-mentioned creaking and scratch resistance can be realized. From these viewpoints, the content of the matting agent in the cellulose acylate film is particularly preferably 0.05 to 1.0% by mass.

<Configuration and physical properties of cellulose acylate film>
(Layer structure of film)
The cellulose acylate film of the present invention may be a single layer or a laminate of two or more layers.
When the cellulose acylate film of the present invention is a laminate of two or more layers, a two-layer structure or a three-layer structure is more preferable, and a three-layer structure is preferable. The three-layer structure is preferably composed of one core layer (hereinafter also referred to as a base layer) and skin layers (skin A layer and skin B layer) facing each other across the core layer (skin B). Layer / core layer / skin A layer).
The skin A layer and the skin B layer are collectively referred to as a skin layer (or surface layer).

  In the cellulose acylate film of the present invention, the acyl substitution degree of the cellulose acylate in each layer may be uniform, or a plurality of cellulose acylates may be mixed in one layer, but the cellulose acylate in each layer It is preferable from the viewpoint of adjusting optical properties that the acyl substitution degree is all constant. In addition, when the cellulose acylate film of the present invention has a three-layer structure, it is preferable from the viewpoint of production cost that the cellulose acylate contained in the surface layers on both sides is a cellulose acylate having the same acyl substitution degree.

(Film thickness)
10-100 micrometers is preferable, as for the average film thickness of the cellulose acylate film of this invention, 15-80 micrometers is more preferable, and 20-70 micrometers is more preferable. By making it 20 μm or more, the handling property when producing a web-like film is improved, which is preferable. Moreover, by setting it as 70 micrometers or less, it is easy to respond to a humidity change and it is easy to maintain an optical characteristic.
Moreover, when the cellulose acylate film of the present invention has a laminated structure of three or more layers, the thickness of the core layer is preferably 3 to 70 μm, and more preferably 5 to 60 μm. When the film of the present invention has a laminated structure of three or more layers, the thickness of the surface layers (skin A layer and skin B layer) on both sides of the film is more preferably 0.5 to 20 μm, particularly 0.5 to 10 μm. Preferably, 0.5 to 3 μm is most preferable.

<Method for producing cellulose acylate film>
Although the manufacturing method of the cellulose acylate film of the present invention is not particularly limited, it is preferably manufactured by a melt film forming method or a solution film forming method, and more preferably manufactured by a solution film forming method. In carrying out the solution casting method, a known apparatus can be used according to a conventional method. Specifically, the dope (polymer solution) prepared in a dissolving machine (kettle) is filtered, and then temporarily stored in a storage kettle, and the foam contained in the dope is defoamed for final preparation. The dope is kept at 30 ° C., and is sent from the dope discharge port to the pressure die through a pressure metering gear pump capable of delivering a constant amount of liquid with high accuracy, for example, by the rotational speed, and the dope runs endlessly from the die (slit) of the pressure die. It casts uniformly on the metal support body of the casting part which has been (dope casting process). Next, at the peeling point where the metal support has almost gone around, the dough film (web) which has been dried is peeled from the metal support, and then transported to the drying zone, and drying is completed while being transported by a roll group. As a metal support used in casting, a metal band or a metal drum can be used. Details of the casting process and the drying process of the solution casting film-forming method are also described in pages 120 to 146 of JP-A-2005-104148, and can be applied to the present invention as appropriate.

-Co-casting When producing a laminate of two or more layers, it can be used by appropriately selecting a variety of general casting methods such as co-casting method, sequential casting method, coating method, The co-casting method is particularly preferable from the viewpoints of stable production and production cost reduction.
In the case of producing a cellulose acylate film having two or more layers by the co-casting method, first, a cellulose acetate solution (dope) for each layer is prepared. Subsequently, the dope for each layer is extruded onto a casting support (band or drum) by extruding the dope from a casting giusa having a function of simultaneously extruding the casting dope for each layer from another slit or the like. The film is cast at the same time, peeled off from the support at an appropriate time, and dried to form a film. FIG. 2 is a cross-sectional view showing a state in which the co-casting giesser 3 is used to simultaneously extrude and cast the surface layer dope 1 and the core layer dope 2 on the casting support 4.

(Extension process)
In the manufacturing method of the cellulose acylate film of this invention, it is preferable to include the process of extending | stretching formed into a film. The stretching direction of the cellulose acylate film may be either the film transport direction and the direction (width direction) orthogonal to the transport direction, but the film that follows is used to be the direction (width direction) orthogonal to the film transport direction. It is preferable from the viewpoint of the polarizing plate processing process.

  Methods for stretching in the width direction are described in, for example, JP-A-62-115035, JP-A-4-152125, JP-A-2842211, JP-A-298310, and JP-A-11-48271. Yes. In the case of stretching in the longitudinal direction, for example, the film is stretched by adjusting the speed of the film transport roller so that the film winding speed is higher than the film peeling speed. In the case of stretching in the width direction, the film can also be stretched by conveying while holding the width of the film with a tenter and gradually widening the width of the tenter. After the film is dried, it can be stretched using a stretching machine (preferably uniaxial stretching using a long stretching machine).

  Stretching in the width direction is preferably 5 to 100%, more preferably 5 to 80%, particularly preferably 5 to 40%. In addition, unstretched means that stretching is 0%. The stretching process may be performed in the middle of the film forming process, or the original fabric that has been formed and wound may be stretched. In the former case, stretching may be performed in a state including the residual solvent amount, and the residual solvent amount = (residual volatile matter mass / heat-treated film mass) × 100% is preferably stretched at 0.05 to 50%. be able to. It is particularly preferable to perform 5 to 80% stretching in a state where the residual solvent amount is 0.05 to 5%.

(Anti-glare layer)
In the antiglare film of the present invention, an antiglare layer is provided on the above-described cellulose acylate film, and the thickness of the antiglare layer is 3.0 μm or more and 7.0 μm or less, and the antiglare layer is at least a) cured. And b) resin particles, and c) a photopolymerization initiator. The content of b) is 3% by mass or more and 10% by mass with respect to the solid content in the photocurable composition. The content of c) is 1.5% by mass or more and 5% by mass or less.
The antiglare layer can be formed for the purpose of imparting to the film an antiglare property due to surface scattering and preferably a hard coat property for improving the hardness and scratch resistance of the film.

<A) Curable compound>
The photocurable composition for forming the antiglare layer in the present invention contains at least one curable compound. The curable compound becomes a translucent resin after curing and preferably functions as a binder resin that forms a matrix constituting the antiglare layer.

  As the curable compound, a monomer having two or more ethylenically unsaturated groups is preferable. Monomers include esters of polyhydric alcohol and (meth) acrylic acid {eg, ethylene glycol di (meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate , Trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa ( Meth) acrylate, 1,2,3-chlorohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate}, vinylbenzene and Derivatives such as 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone, vinylsulfone (eg divinylsulfone), (meth) acrylamide (eg methylenebis) Acrylamide) and the like. Commercially available polyfunctional acrylate compounds having a (meth) acryloyl group can be used, such as KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd., PET-30, Shin Nakamura Chemical Co., Ltd., NK Ester A -TMMT, A-TMPT, etc. can be mentioned. From the viewpoint of reducing curling shrinkage and suppressing curling, it is preferable to add ethylene oxide, propylene oxide, or caprolactone to increase the distance between crosslinking points. For example, trimethylolpropane triacrylate (for example, Osaka Organic Chemical Co., Ltd.) added with ethylene oxide Biscoat V # 360), glycerin propylene oxide-added triacrylate (for example, V # GPT manufactured by Osaka Organic Chemical Co., Ltd.), caprolactone-added dipentaerythritol hexaacrylate (for example, Nippon Kayaku DPCA-20, 120) and the like are preferably used. Two or more types of monomers having two or more ethylenically unsaturated groups are also preferably used in combination.

Further, as the curable compound, a resin having two or more ethylenically unsaturated groups, for example, a relatively low molecular weight polyester resin, polyether resin, acrylic resin, epoxy resin, urethane resin, alkyd resin, spiroacetal resin Also, oligomers or prepolymers such as polyfunctional compounds such as polybutadiene resins, polythiol polyene resins and polyhydric alcohols may be mentioned. Two or more of these oligomers or prepolymers may be used in combination.
The resin having two or more ethylenically unsaturated groups is preferably contained in an amount of 10 to 100% by mass based on the total amount of the curable compound.

  Polymerization of these monomers having an ethylenically unsaturated group can be performed by irradiation with ionizing radiation in the presence of a radical photopolymerization initiator.

  The curable compound used in the present invention may be one type or two or more types. The content of the curable compound is preferably 60 to 99% by mass, preferably 70 to 97% by mass, based on the total solid content of the curable composition for forming the antiglare layer, from the viewpoint of the film strength of the antiglare layer. Is more preferable, and 80-95 mass% is still more preferable.

In the present invention, the refractive index of the antiglare layer excluding the translucent particles is preferably 1.46 to 1.65, and more preferably 1.49 to 1.60. By setting the refractive index within this range, coating unevenness and interference unevenness can be made inconspicuous and an antiglare layer having high hardness can be obtained.
Here, the refractive index of the film of the antiglare layer excluding the translucent particles can be quantitatively evaluated by directly measuring with an Abbe refractometer or measuring a spectral reflection spectrum or a spectral ellipsometry.

<B) Resin particles>
The photocurable composition for forming the antiglare layer contains at least one resin particle. The average particle diameter of the resin particles is preferably 2 μm to 6 μm.

  Specific examples of the resin particles include, for example, crosslinked polymethyl methacrylate particles, crosslinked methyl methacrylate-styrene copolymer particles, crosslinked polystyrene particles, crosslinked methyl methacrylate-methyl acrylate copolymer particles, crosslinked acrylate-styrene copolymer particles, Examples thereof include resin particles such as melamine / formaldehyde resin particles and benzoguanamine / formaldehyde resin particles. Of these, crosslinked styrene particles, crosslinked polymethyl methacrylate particles, crosslinked methyl methacrylate-styrene copolymer particles, and the like are preferable. Furthermore, the surface of these resin particles is surface-modified particles in which a compound containing fluorine atom, silicon atom, carboxyl group, hydroxyl group, amino group, sulfonic acid group, phosphoric acid group, etc. is chemically bonded, or nano-sized such as silica or zirconia. Examples of the particles include inorganic fine particles bonded to the surface.

  Two or more kinds of resin particles having different particle diameters may be used in combination. It is possible to impart anti-glare properties with resin particles having a larger particle size and to impart other optical characteristics with resin particles having a smaller particle size.

Further, from the viewpoint of adjusting internal haze and surface haze, the absolute value of the difference between the refractive index of the binder and the refractive index of the resin particles is preferably 0.040 or less. The absolute value of the difference between the refractive index of the binder and the refractive index of the resin particles is preferably 0.030 or less, more preferably 0.020 or less, and still more preferably 0.015 or less. As a combination of the resin particles and the binder, for example, a binder (having a refractive index after curing of 1.55 to 1.70) mainly composed of a tri- or higher functional (meth) acrylate monomer and a styrene content of 50 to 100 mass. % Cross-linked methyl methacrylate-styrene copolymer particles and / or combinations of benzoguanamine particles, and among these, the above-mentioned binder and cross-linked methyl methacrylate having a styrene content of 50 to 100% by mass -Combinations with styrene copolymer particles (refractive index of 1.54 to 1.59) are preferably exemplified.
The refractive index of the translucent particles is determined by measuring the turbidity by dispersing the same amount of the translucent particles in the solvent in which the refractive index is changed by changing the mixing ratio of two kinds of solvents having different refractive indexes. It is measured by measuring the refractive index of the solvent when the degree becomes minimum with an Abbe refractometer.

  In the antiglare film of the present invention, the content of b) resin particles with respect to the solid content in the photocurable composition is 3% by mass or more and 10% by mass or less, preferably 3% by mass or more and 8.5% by mass or less. is there. When there is more content than 10 mass%, when the anti-glare film of this invention is used as a polarizing plate protective film, polarizer durability will deteriorate. On the other hand, if it is less than 3% by mass, the antiglare effect cannot be obtained sufficiently.

<C) Photopolymerization initiator>
The photocurable composition for forming the antiglare layer contains a photopolymerization initiator.
Specific examples of the photopolymerization initiator include acetophenones, benzoins, benzophenones, ketals, anthraquinones, thioxanthones, azo compounds, peroxides (JP-A No. 2001-139663, etc.), 2,3- Examples thereof include dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, and coumarins. In addition, it is also preferable to use a phosphine oxide photopolymerization initiator in order to promote curing inside the antiglare layer.

The phosphine oxide photopolymerization initiator preferably has an n-π * transition at the time of light absorption and has a photobleaching effect. Specifically, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis ( Preferred is 2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
Examples of commercially available phosphine oxide photopolymerization initiators include BASF Irgacure 819, DAROCUR TPO, and the like.
The phosphine oxide photopolymerization initiator used in the present invention may be one type or two or more types.

  Examples of acetophenones include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxy-dimethylphenylketone, 1-hydroxy-dimethyl-p-isopropylphenylketone, 1-hydroxy Cyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 4-phenoxydichloroacetophenone, 4-t- Butyl-dichloroacetophenone is included.

Examples of benzoins include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. It is.
Examples of benzophenones include benzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone, 4,4'-dimethylaminobenzophenone (Michler ketone), 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone and the like are included.

Examples of the borate salt are described in Japanese Patent Nos. 2764769 and 2002-116539, and in Kunz, Martin “Rad Tech'98. Proceeding April 19-22, 1998, Chicago”. Organic borate. For example, the compounds described in paragraphs [0022] to [0027] of JP-A-2002-116539 are mentioned.
Other organic boron compounds include JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, and JP-A-7-292014. Specific examples thereof include organoboron transition metal coordination complexes such as ionic complexes with cationic dyes.

Examples of the active esters include 1,2-octanedione, 1- [4- (phenylthio) -1,2- (O-benzoyloxime)], sulfonic acid esters, cyclic active ester compounds, and the like.
Specifically, Examples 1 to 21 described in JP-A No. 2000-80068 are particularly preferable.
Examples of onium salts include aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts.

As the active halogens, specifically, “Bull Chem. Soc” by Wakabayashi et al.
Japan, 42, 2924 (1969), U.S. Pat. No. 3,905,815, JP 5-27830, MP Hutt “Jurnal of Heterocyclic Chemistry”, Vol. 1 (3), ( 1970) and the like, and in particular, an oxazole compound substituted with a trihalomethyl group: an s-triazine compound.
More preferable examples include s-triazine derivatives in which at least one mono, di, or trihalogen-substituted methyl group is bonded to the s-triazine ring.

  Commercially available radical photopolymerization initiators include KAYACURE (DETX-S, BP-100, BDKM, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, ITX, QTX, BTC, manufactured by Nippon Kayaku Co., Ltd. MCA, etc.), BASF Irgacure (651, 184, 500, 907, 369, 1173, 1870, 2959, 4265, 4263, 127, etc.), DAROCUR (1173), Esacure (KIP100F, KB1, EB3, manufactured by Sartomer) BP, X33, KT046, KT37, KIP150, TZT) and combinations thereof and the like are preferable examples.

  The content of c) photopolymerization initiator based on the solid content in the photocurable composition for forming the antiglare layer is 1.5% by mass or more and 5% by mass or less, preferably 1.5% by mass or more and 3%. It is below mass%. When the content is more than 5% by mass, the durability of the polarizer is deteriorated when the antiglare film of the present invention is used as a polarizing plate protective film. On the other hand, when the content is less than 1.5% by mass, the hardness of the film becomes insufficient.

<Solvent>
The photocurable composition for forming the antiglare layer may further contain a solvent. The solvent is selected from the viewpoints of being able to dissolve or disperse each component, easily forming a uniform surface in the coating process and the drying process, ensuring liquid storage stability, having an appropriate saturated vapor pressure, and the like. Various solvents can be used.
Two or more kinds of solvents can be mixed and used. In particular, from the viewpoint of drying load, it is preferable that the main component is a solvent having a boiling point of 100 ° C. or lower at normal pressure and room temperature, and a small amount of solvent having a boiling point of more than 100 ° C. is included for adjusting the drying speed.
In the photocurable composition for forming the antiglare layer, it is preferable to contain 30-80% by mass of a solvent having a boiling point of 80 ° C. or less in the total solvent of the coating composition in order to prevent sedimentation of the resin particles. It is still more preferable to contain 50-70 mass. By setting the ratio of the solvent having a boiling point of 80 ° C. or less to the above ratio, the penetration of the resin component into the transparent support is moderately suppressed, and the rate of increase in the viscosity due to drying is increased, whereby the particle sedimentation can be suppressed.

  Examples of the solvent having a boiling point of 100 ° C. or lower include hydrocarbons such as hexane (boiling point 68.7 ° C.), heptane (98.4 ° C.), cyclohexane (80.7 ° C.), benzene (80.1 ° C.), Halogenated carbonization such as dichloromethane (39.8 ° C), chloroform (61.2 ° C), carbon tetrachloride (76.8 ° C), 1,2-dichloroethane (83.5 ° C), trichloroethylene (87.2 ° C) Hydrogens, diethyl ether (34.6 ° C), diisopropyl ether (68.5 ° C), dipropyl ether (90.5 ° C), tetrahydrofuran (66 ° C) and other ethers, ethyl formate (54.2 ° C), Esters such as methyl acetate (57.8 ° C.), ethyl acetate (77.1 ° C.), isopropyl acetate (89 ° C.), acetone (56.1 ° C.), 2-butanone (methyl ethyl) Ketones such as 79.6 ° C, the same as ketone, methanol (64.5 ° C), ethanol (78.3 ° C), 2-propanol (82.4 ° C), 1-propanol (97.2 ° C), etc. Alcohols, cyano compounds such as acetonitrile (81.6 ° C.), propionitrile (97.4 ° C.), carbon disulfide (46.2 ° C.), and the like. Of these, ketones and esters are preferable, and ketones are particularly preferable. Among the ketones, 2-butanone is particularly preferable.

  Examples of the solvent having a boiling point exceeding 100 ° C. include octane (125.7 ° C.), toluene (110.6 ° C.), xylene (138 ° C.), tetrachloroethylene (121.2 ° C.), chlorobenzene (131.7 ° C.), Dioxane (101.3 ° C.), dibutyl ether (142.4 ° C.), isobutyl acetate (118 ° C.), cyclohexanone (155.7 ° C.), 2-methyl-4-pentanone (same as MIBK, 115.9 ° C.), Examples thereof include 1-butanol (117.7 ° C.), N, N-dimethylformamide (153 ° C.), N, N-dimethylacetamide (166 ° C.), dimethyl sulfoxide (189 ° C.) and the like. Cyclohexanone and 2-methyl-4-pentanone are preferable.

<Other additives>
(Surfactant)
In the photocurable composition for forming the antiglare layer, in order to ensure surface uniformity such as coating unevenness, drying unevenness, point defect, etc., any one of fluorine-based and silicone-based surfactants, Or it is preferable to contain both. In particular, a fluorine-based surfactant can be preferably used because an effect of improving surface defects such as coating unevenness, drying unevenness, and point defects appears at a smaller addition amount. Productivity can be improved by giving high-speed coating suitability while improving surface uniformity.

  Preferable examples of the fluorosurfactant include a fluoroaliphatic group-containing copolymer (hereinafter sometimes abbreviated as “fluorine polymer”), and the fluoropolymer is a monomer of the following (i): An acrylic resin, a methacrylic resin, and a copolymer that can be copolymerized with the repeating unit corresponding to the monomer (i) and the repeating unit corresponding to the monomer (ii) below. Copolymers with vinyl monomers are useful.

(I) Fluoroaliphatic group-containing monomer represented by the following general formula A

In the general formula A, R ¹⁰¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom, a sulfur atom or —N (R ¹⁰² ) —, m is an integer of 1-6, and n is an integer of 2-4. Represent. R ¹⁰² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically a methyl group, an ethyl group, a propyl group, or a butyl group, and preferably a hydrogen atom or a methyl group. X is preferably an oxygen atom.

(Ii) Monomer represented by the following general formula (b) copolymerizable with the above (i)

In general formula B, R ¹⁰³ represents a hydrogen atom or a methyl group, Y represents an oxygen atom, a sulfur atom or —N (R ¹⁰⁵ ) —, R ¹⁰⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically Specifically, it represents a methyl group, an ethyl group, a propyl group or a butyl group, preferably a hydrogen atom or a methyl group. Y is an oxygen atom, -N (H) -, and -N (CH ₃₎ - are preferred.
R ¹⁰⁴ represents a linear, branched or cyclic alkyl group having 4 to 20 carbon atoms which may have a substituent. As the substituent of the alkyl group of R14, a hydroxyl group, an alkylcarbonyl group, an arylcarbonyl group, a carboxyl group, an alkyl ether group, an aryl ether group, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, An amino group and the like can be mentioned, but not limited thereto. Examples of the linear, branched or cyclic alkyl group having 4 to 20 carbon atoms include a butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and undecyl group which may be linear or branched. , Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group, eicosanyl group, etc., and monocyclic cycloalkyl groups such as cyclohexyl group, cycloheptyl group and bicycloheptyl group, bicyclodecyl group, tricycloundecyl group, Polycyclic cycloalkyl groups such as a tetracyclododecyl group, an adamantyl group, a norbornyl group, a tetracyclodecyl group, and the like are preferably used.

  The amount of the fluoroaliphatic group-containing monomer represented by the general formula (a) used in the fluorine-based polymer is 10 mol% or more based on each monomer of the fluorine-based polymer, preferably 15 to 70 mol%. More preferably, it is the range of 20-60 mol%.

  The preferred weight average molecular weight of the fluoropolymer is preferably 3000 to 100,000, more preferably 5,000 to 80,000. Furthermore, the preferable addition amount of the fluoropolymer used in the present invention is in the range of 0.001 to 5 parts by mass, more preferably in the range of 0.005 to 3 parts by mass with respect to 100 parts by mass of the coating solution. More preferably, it is the range of 0.01-1 mass part. If the addition amount of the fluorine-based polymer is 0.001 part by mass or more, the effect of adding the fluorine-based polymer is sufficiently obtained, and if the addition amount is 5 parts by mass or less, the coating film cannot be sufficiently dried or applied. There is no problem of adversely affecting the performance as a film (for example, reflectance, scratch resistance).

(Dispersant)
The antiglare layer may contain a copolymer having an amine value of 1 to 30 mgKOH / g as a dispersant. A copolymer can be contained in the photocurable composition for forming the antiglare layer.
The amount added to the antiglare layer or the photocurable composition is preferably 0.01 to 5.0 mass%, more preferably 0.1 to 3.0 mass%, based on the resin particles. In the copolymer, an amine group acts as an adsorbing group, and adsorbs on the surface of the resin particle to give steric hindrance between the resin particles. It is estimated that this increases the dispersibility of the particles and facilitates the formation of dense irregularities.

  An example of a specific compound of the copolymer having an amine value of 1 to 30 mgKOH / g in the present invention is not particularly limited as long as the physical property values described above are satisfied. Preferred examples of this compound include commercially available wetting and dispersing agents such as a wetting and dispersing agent manufactured by BYK Chemie, Disperbyk-161 (11), Disperbyk-162 (13), Disperbyk-163 (10). Disperbyk-164 (18), Disperbyk-166 (20), Disperbyk-167 (13), Disperbyk-168 (11), Disperbyk-182 (13), Disperbyk-183 (17), Disperbyk-184 (15), Disperbyk-185 (17), Disperbyk-2000 (4), Disperbyk-2001 (29), Disperbyk-2009 (4), Disperbyk-2050 (30), Disper yk-2070 (20) and the like, Ajinomoto Fine Techno Co., Ltd. pigment dispersant, Ajisper PB881, etc., or Enomoto Kasei Co., Ltd. pigment dispersant, Disparon DA-703-50, Disparon DA-325, Disparon DA -7301, disparon 1860, disparon 7004, etc. can be used. In the above, the value in () is the amine value (KOH / g). Among these, modified acrylic block copolymers are preferable from the viewpoint of side effects on particle dispersibility and film transparency, and among them, Disperbyk-2000 and Disperbyk-166 are particularly effectively used. Although the copolymer mentioned above may be used independently, you may use 2 or more types together.

  The dispersion method of the resin particles is not particularly limited, but a known disperser, that is, a disperser such as a ball mill, a roll mill, a bead mill, a high-speed disperser, a polytron disperser, a dissolver, a magnetic stirrer, an ultrasonic disperser or the like is used. Can be prepared. In particular, it is particularly preferable to disperse with a polytron disperser, dissolver, magnetic stirrer or ultrasonic disperser. As a dispersion method, it is preferable to disperse an organic solvent and resin particles in the disperser and then add and disperse a copolymer having an amine value of 1 to 30 mgKOH / g.

(Smectite type clay organic complex)
Further, in the present invention, in order to control the cohesiveness of the resin particles, an embodiment using a smectite clay organic composite obtained by intercalating a quaternary ammonium salt to the smectite clay is also preferably exemplified. The The content of the smectite-type clay organic complex is preferably 0.2 to 8.0% by mass, more preferably 0.3 to 4.0% by mass, based on the total solid content of the formed antiglare layer. 0.4-3.0 mass% is further more preferable, and 0.5-2.0 mass% is especially preferable.

The quaternary ammonium salt is preferably a quaternary ammonium salt represented by the following general formula (201).
[(R ²⁰¹ ) ₃ (R ²⁰² ) N] ⁺ · X ⁻ (201)
(In General Formula (201), R ²⁰¹ and R ²⁰² are not the same, R ²⁰¹ represents an alkyl group, an alkenyl group, or an alkynyl group having 4 to 24 carbon atoms, and R ²⁰² represents an alkyl having 1 to 10 carbon atoms. A group, an alkenyl group or an alkynyl group, and X- represents an anion.)

  Examples of the quaternary ammonium ion represented by the general formula (201) include trioctyl, methyl, ammonium ion, tristearyl, ethyl, ammonium ion, trioctyl, ethyl, ammonium ion, tristearyl, methyl, ammonium ion, tridecyl, Hexyl / ammonium ion, tritetradecyl / propyl / ammonium ion and the like can be mentioned, and among these, trioctyl / methyl / ammonium ion and tristearyl / ethyl / ammonium ion are preferably exemplified.

In general formula (201), X < ^- > represents an anion. Examples of such anions include Cl ⁻ , Br ⁻ , OH ⁻ , NO ₃ ^{— and the} like, and among these, Cl ⁻ is preferably exemplified.

  Examples of commercially available smectite-type clay organic composites include Lucentite SAN, Lucentite STN, Lucentite SEN, and Lucentite SPN (manufactured by Coop Chemical Co., Ltd.). These can be used alone or in combination of two or more. it can.

  In addition to the above, known additives described in JP-A-2015-4979 can be appropriately used as long as the effects of the present invention are not impaired.

  In the antiglare film of the present invention, the thickness of the antiglare layer is from 3.0 μm to 7.0 μm, and preferably from 3.0 μm to 5.0 μm. If it is thicker than 7.0 μm, the content of the resin particles and the photopolymerization initiator contained in the antiglare layer is increased. As a result, when the antiglare film of the present invention is used as a polarizing plate protective film, the durability of the polarizer deteriorates. End up. On the other hand, if the thickness is less than 3.0 μm, the hardness of the film becomes insufficient.

  The 20 ° glossiness of the antiglare film in the present invention is preferably 30 or more and 80 or less, more preferably 40 or more and 70 or less. When the glossiness is less than 30, the antiglare property is too strong and conversely deteriorates the visibility. When the glossiness is higher than 80, the antiglare property is too weak and the antiglare performance is not sufficient. The glossiness of the antiglare film can be measured according to JIS-Z8741.

  The strength of the antiglare film in the present invention is preferably 2H or more in a pencil hardness test according to JIS-K5400.

[Layer structure of anti-glare film]
The antiglare film of the present invention has a simplest structure in which an antiglare layer is coated on a cellulose acylate film.

  Although the example of the preferable layer structure of the anti-glare film of this invention is shown below, it is not necessarily limited only to these layer structures.

-Cellulose acylate film / antiglare layer- Cellulose acylate film / antiglare layer / hard coat layer- Cellulose acylate film / antiglare layer / low refractive index layer- Cellulose acylate film / antiglare layer / hard coat layer / Low refractive index layer

[Production method of anti-glare film]
The method for producing an antiglare film of the present invention is a compound represented by the above general formula (1), wherein a photocurable composition containing at least a) a curable compound, b) resin particles, and c) a photopolymerization initiator is represented. And a step of coating on a cellulose acylate film containing a sugar ester compound and curing to form an antiglare layer.

The photocurable composition is preferably applied by a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, or a die coating method. A coating method and a die coating method (see US Pat. No. 2,681,294 and JP-A-2006-122889) are more preferred, and a die coating method is particularly preferred.
You may heat and dry, after apply | coating a photocurable composition.

[Curing conditions for anti-glare layer]
Preferred examples of the method for curing the antiglare layer in the present invention are described below.
In the present invention, it is effective to cure by combining irradiation with ionizing radiation and heat treatment before, at the same time as, or after irradiation.
Although the pattern of some manufacturing processes is shown below, it is not limited to these.
Before irradiation → At the same time as irradiation → After irradiation (-indicates that heat treatment is not performed)
(1) Heat treatment → Ionizing radiation curing → −
(2) Heat treatment → Ionizing radiation curing → Heat treatment (3) − → Ionizing radiation curing → Heat treatment In addition, a step of performing heat treatment simultaneously with ionizing radiation curing is also preferable.

  In the present invention, as described above, heat treatment is preferably performed in combination with irradiation with ionizing radiation. The heat treatment is not particularly limited as long as it does not damage the support layer of the antiglare film and the constituent layers including the antiglare layer, but is preferably 60 to 200 ° C, more preferably 80 to 130 ° C, and most preferably 80 to 130 ° C. 110 ° C.

  The time required for the heat treatment is 15 seconds to 1 hour, preferably 30 seconds to 30 minutes, and most preferably 45 seconds to 5 minutes, although it varies depending on the molecular weight of the components used, interaction with other components, viscosity, and the like.

There is no restriction | limiting in particular about the kind of ionizing radiation, Although an X-ray, an electron beam, an ultraviolet-ray, visible light, infrared rays etc. are mentioned, an ultraviolet-ray is used widely. For example, if the coating film is UV curable, it is to cure each layer by irradiating an irradiation amount of ultraviolet rays of 10mJ ^/ cm ² ~1000mJ ^/ cm 2 by an ultraviolet lamp preferred. At the time of irradiation, the above-mentioned energy may be applied at once, or irradiation may be performed in divided portions. In particular, from the viewpoint of reducing in-plane performance variation and improving the surface texture and surface roughness, it is preferable to irradiate in two or more times, and initially 150 mJ / cm. ^{It is} preferable to irradiate ultraviolet light with a low irradiation amount of ² or less, and then irradiate ultraviolet light with a high irradiation amount of 50 mJ / cm ² or more, and to apply a higher irradiation amount later than the initial stage.

[Other layers]
In the antiglare film of the present invention, the following layers can be provided on the cellulose acylate film in addition to the antiglare layer.

[High refractive index layer, medium refractive index layer, and low refractive index layer]
The refractive index of the high refractive index layer is preferably 1.70 to 1.74, more preferably 1.71 to 1.73. The refractive index of the middle refractive index layer is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the medium refractive index layer is preferably 1.60 to 1.64, and more preferably 1.61 to 1.63. The low refractive index layer preferably has a refractive index of 1.30 to 1.47. In the case of a multilayer thin film interference type antireflection film (medium refractive index layer / high refractive index layer / low refractive index layer), the refractive index of the low refractive index layer is preferably 1.33-1.38. More preferably, it is 35-1.37.
The high refractive index layer, medium refractive index layer, and low refractive index layer are formed by a chemical vapor deposition (CVD) method or a physical vapor deposition (PVD) method, particularly a vacuum vapor deposition method or a sputtering method, which is a kind of physical vapor deposition method, and an inorganic substance. Although a transparent oxide thin film can be used, a method using all wet coating is preferred.
As the high refractive index layer, the medium refractive index layer, and the low refractive index layer, those described in paragraphs [0197] to [0211] of JP-A-2009-98658 can be used.

  These layers are preferably formed on the antiglare layer, and the material and thickness are preferably adjusted as appropriate.

<< Polarizing plate >>
The polarizing plate of the present invention has at least a polarizer and the antiglare film of the present invention.
The polarizing plate of the present invention preferably has a polarizer and the film of the present invention on one or both sides of the polarizer. Examples of the polarizer include an iodine polarizer, a dye polarizer using a dichroic dye, and a polyene polarizer. The iodine polarizer and the dye polarizer are generally produced using a polyvinyl alcohol film. When using the anti-glare film of this invention as a polarizing plate protective film, the preparation methods of a polarizing plate are not specifically limited, It can produce by a general method. There is a method in which the obtained antiglare film is treated with an alkali and bonded to both surfaces of a polarizer prepared by immersing and stretching a polyvinyl alcohol film in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution. Instead of alkali treatment, easy adhesion processing as described in JP-A-6-94915 and JP-A-6-118232 may be performed. Examples of the adhesive used to bond the protective film-treated surface and the polarizer include polyvinyl alcohol adhesives such as polyvinyl alcohol and polyvinyl butyral, vinyl latexes such as butyl acrylate, and the like.

  The method of bonding the antiglare film of the present invention to the polarizer is preferably performed such that the transmission axis of the polarizer and the slow axis of the antiglare film of the present invention are substantially orthogonal. In the liquid crystal display device of the present invention, it is preferable that the transmission axis of the polarizing plate and the slow axis of the antiglare film of the present invention are substantially orthogonal. Here, being substantially orthogonal means that the direction of the main refractive index nx of the antiglare film of the present invention and the direction of the transmission axis of the polarizing plate intersect at an angle of 90 ° ± 10 °. It is preferable that they intersect at an angle of 90 ° ± 5 °, more preferably at an angle of 90 ° ± 1 °. By adjusting the angle in this way at the time of bonding, light leakage under a polarizing plate crossed Nicol can be further reduced. The slow axis can be measured by various known methods, for example, using a birefringence meter (KOBRA DH, manufactured by Oji Scientific Instruments).

  The polarizing plate of the present invention is produced not only in the form of a film piece cut into a size that can be incorporated into a liquid crystal display device as it is, but also in a long shape by continuous production and wound up into a roll. The polarizing plate of the aspect (for example, roll length 2500m or more or 3900m or more aspect) is also included. In order to use for a large-screen liquid crystal display device, the width of the polarizing plate is preferably 1470 mm or more. The specific configuration of the polarizing plate of the present invention is not particularly limited, and a known configuration can be employed. For example, the configuration described in FIG. 6 of JP-A-2008-262161 can be employed.

<< Liquid Crystal Display >>
The liquid crystal display device of the present invention has a liquid crystal cell and the polarizing plate of the present invention.
The liquid crystal display device of the present invention is a liquid crystal display device having a liquid crystal cell and a pair of polarizing plates disposed on both sides of the liquid crystal cell, wherein at least one of the polarizing plates is the polarizing plate of the present invention, IPS, OCB or VA. A liquid crystal display device in a mode is preferable. The internal structure of a typical liquid crystal display device is shown in FIG. There is no restriction | limiting in particular as a concrete structure of the liquid crystal display device of this invention, A well-known structure is employable. Further, the configuration described in FIG. 2 of JP-A-2008-262161 can also be preferably employed.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not construed as being limited thereto.

[Synthesis of Compound Represented by General Formula (1)]
The compound represented by the general formula (1) of the present invention was synthesized as follows.
Synthesis examples of typical compounds are shown below.

  Illustrative compound (A-4) can be synthesized, for example, by the following reaction scheme.

Synthesis example 1
(A) Synthesis of Exemplified Compound (A-4) in Route 1 Exemplified Compound (A-4) was synthesized as follows.

1) Synthesis of intermediate N-benzyl-N'-phenylurea A 5 L glass flask equipped with a thermometer, reflux condenser and stirrer was charged with 321 g of benzylamine and 2 L of acetonitrile, cooled in a water bath and stirred with isocyanide. 358 g of phenyl acid was added dropwise at such a rate that the internal temperature of the reaction solution became 40 ° C. or lower. After stirring for 2 hours as it was, 2 L of water was added and suction filtered, and the precipitated crystals were collected by filtration and washed 3 times with 1 L of water. The obtained crystals were dried at 80 ° C. under reduced pressure to obtain 610 g of an intermediate N-benzyl-N′-phenylurea.
The structure of the obtained compound was confirmed by ¹ H-NMR spectrum.
¹ H-NMR (300 MHz, DMSO-d6), δ: 8.52 (s, 1H), 7.45-7.18 (m, 9H), 6.89 (t, 1H), 6.59 (s) , 1H), 4.30 (d, 2H)

2) Synthesis of Exemplary Compound (A-4) Into a 300 ml glass flask equipped with a thermometer, a reflux condenser and a stirrer, 5.0 g of intermediate N-benzyl-N′-phenylurea and benzylmalonic acid 4 g, 10 mL of toluene and 15 mL of acetic anhydride were charged, and the mixture was heated with stirring so that the internal temperature became 75 ° C., and the stirring was continued at 75 ° C. for 2 hours. Thereafter, the mixture was cooled to 50 ° C., and 50 mL of a 1 mol / dm ³ aqueous sodium hydroxide solution was added. The organic phase was discarded, and the aqueous phase was cooled in an ice water bath, and 10 mL of 6M hydrochloric acid was added dropwise with stirring. Furthermore, after stirring at 0 ° C. for 1 hour, the crystals precipitated by suction filtration were collected by filtration, washed with water and dried to obtain 7.5 g of exemplary compound (A-4).
The structure of the obtained compound was confirmed by ¹ H-NMR spectrum.
¹ H-NMR (300 MHz, CDCl ₃ ), δ: 7.55 to 7.20 (m, 9H), 7.13 (t, 2H), 6.96 (d, 2H), 6.84 (br, 2H), 4.96 (s, 2H), 3.94 (t, 1H), 3.55 (m, 2H)

Synthesis example 2
(B) Synthesis of Exemplified Compound (A-4) in Route 2 Exemplified Compound (A-4) was synthesized as follows.

1) Synthesis of intermediate 1-benzyl-3-phenylbarbituric acid N-benzyl-N'-phenyl synthesized in Synthesis Example 1-1 in a 300 ml glass flask equipped with a thermometer, reflux condenser and stirrer 5.0 g of urea, 2.5 g of malonic acid, 20 mL of toluene, and 5.6 g of acetic anhydride were charged, and the mixture was heated to 80 ° C. while stirring, and the stirring was continued at 80 ° C. for 3 hours. Thereafter, the mixture was cooled to 50 ° C., 15 mL of water was added for liquid separation, and the aqueous phase was discarded. While stirring the organic layer at room temperature, 5 mL of isopropanol was added dropwise. Further, the mixture was stirred at 10 ° C. or lower for 0.5 hour, suction filtered, and the precipitated crystals were collected by filtration, washed with cooled isopropanol, and then dried to obtain 4.6 g of intermediate 1-benzyl-3-phenylbarbituric acid. Obtained.
The structure of the obtained compound was confirmed by ¹ H-NMR spectrum.
¹ H-NMR (300 MHz, CDCl 3), δ: 7.52-7.16 (m, 10H), 5.10 (s, 2H), 3.86 (s, 2H)

2) Synthesis of intermediate 1-benzyl-5-benzylidene-3-phenylbarbituric acid 1-benzyl-3-phenylbarbituric acid in a 300 ml glass flask equipped with a thermometer, reflux condenser and stirrer 0 g, 1.6 g of benzaldehyde and 40 mL of acetic acid were added, 1 drop of sulfuric acid was added, and the mixture was heated with stirring so that the internal temperature became 100 ° C., and the stirring was continued at 100 ° C. for 3 hours. Thereafter, the mixture was cooled to 50 ° C., a mixed solution of 39 mL of isopropanol and 17 mL of water was added, and the mixture was stirred at 10 ° C. or lower for 1 hour, suction filtered, and the precipitated crystals were collected by filtration, washed with methanol, intermediate 1-benzyl- 3.9 g of 5-benzylidene-3-phenylbarbituric acid was obtained.
The structure of the obtained compound was confirmed by ¹ H-NMR spectrum.
¹ H-NMR (300 MHz, CDCl ₃ ), δ: 8.70 (s, 1H), 8.10 (d, 2H), 7.58-7.20 (m, 15H), 5.20 (s, 2H)

3) Synthesis of Exemplified Compound (A-4) Into a 50 ml autoclave was charged 3.5 g of 1-benzyl-5-benzylidene-3-phenylbarbituric acid and 8 mL of methanol, and 0.1 g of Pd-C (10%) was added. While stirring, H ₂ was charged and heated to an internal temperature of 50 ° C., and stirring was continued at 50 ° C. for 3 hours. Thereafter, Pd-C was separated by filtration, cooled to 5 ° C., further added with 4 mL of water, stirred at 5 ° C. for 1 hour, suction filtered and the precipitated crystals were collected by filtration, and mixed with methanol / water = 1/1. After washing with a solvent, it was dried to obtain 3.0 g of exemplary compound (A-4).
The structure of the obtained compound was confirmed by ¹ H-NMR spectrum, IR spectrum and mass spectrum.
In addition, it confirmed that the structure of the obtained compound corresponded with the thing obtained by the synthesis example 1 by the < ¹ > H-NMR spectrum.

  The compounds other than the above used in the examples were synthesized by a method similar to the above, the method described in the aforementioned literature, or a method analogous thereto.

〔Example〕
In the following manner, an antiglare layer was provided on the cellulose acylate film to produce an antiglare film.

<Preparation of cellulose acylate film>
(Preparation of cellulose acylate)
A cellulose acylate having a total degree of acetyl substitution of 2.87 was prepared. This was carried out by adding sulfuric acid (7.8 parts by mass with respect to 100 parts by mass of cellulose) as a catalyst, adding carboxylic acid as a raw material for the acyl substituent, and carrying out an acylation reaction at 40 ° C. In addition, aging was performed at 40 ° C. after acylation. Further, the low molecular weight component of the cellulose acylate was removed by washing with acetone.

(Preparation of surface layer dope)
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a surface dope.

―――――――――――――――――――――――――――――――――――
Composition of surface layer dope ――――――――――――――――――――――――――――――――――――
Cellulose acetate with a total degree of acetyl substitution of 2.87 and a degree of polymerization of 370
100.0 parts by mass Daipet Kogyo Monopet (registered trademark) SB (plasticizer) 3.0 parts by mass Eastman Chemical SAIB-100 (plasticizer) 1.0 part by weight Exemplary compound (A- 4) 6.0 parts by mass Degradation inhibitor-1 0.06 parts by mass Degradation inhibitor-2 0.03 parts by mass Ultraviolet absorber (UV-1) 2.3 parts by mass Silica particles having an average particle size of 20 nm (AEROSIL R972) ,
Nippon Aerosil Co., Ltd. 0.078 parts by mass Methylene chloride (first solvent) 383.7 parts by mass Methanol (second solvent) 83.3 parts by mass n-butanol (third solvent) 3.8 parts by mass ――――――――――――――――――――――――――――――――

  Monopet (registered trademark) SB manufactured by Daiichi Kogyo Kagaku Co. is a benzoic acid ester of sucrose, and SAIB-100 manufactured by Eastman Chemical Co. is an acetic acid and isobutyric acid ester of sucrose.

Deterioration preventive agent-1

Deterioration inhibitor-2

UV-1

(Preparation of dope for base layer)
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a base layer dope.

―――――――――――――――――――――――――――――――――――
Dope for base layer ――――――――――――――――――――――――――――――――――――
Cellulose acetate with a total degree of acetyl substitution of 2.87 and a degree of polymerization of 370
100.0 parts by mass Daipet Kogyo Monopet (registered trademark) SB (plasticizer) 3.0 parts by mass Eastman Chemical SAIB-100 (plasticizer) 1.0 part by weight Exemplary compound (A- 4) 6.0 parts by mass Degradation inhibitor-1 0.06 parts by mass Degradation inhibitor-2 0.03 parts by mass UV absorber (UV-1) 2.3 parts by mass Methylene chloride (first solvent) 298.9 Part by mass Methanol (second solvent) 64.9 parts by mass n-Butanol (third solvent) 2.9 parts by mass ――――――――――――――――――――――― ―――――――――――

(Casting)
Using a drum casting apparatus, the base layer dope prepared as described above and the surface layer dope on both sides of the dope for the stainless steel casting support (support temperature −9 ° C.) are uniformly formed from the casting port. It was cast into. At this time, the flow rate of each dope was adjusted so that the thickness would be skin A layer / core layer / skin B layer = 4 μm / 54 μm / 2 μm. Stripped in a state where the amount of residual solvent in the dope of each layer is about 70% by mass, fixed both ends in the width direction of the film with a pin tenter, and 1.28 in the width direction in a state of residual solvent amount of 3-5% by mass. The film was dried while being stretched twice (28%). Then, it dried further by conveying between the rolls of the heat processing apparatus, and obtained the cellulose acylate film (base material 1). The obtained cellulose acylate film (base material 1) had a thickness of 60 μm and a width of 1480 mm.

  In the above cellulose acylate film (base material 1), cellulose is produced in the same manner as in the cellulose acylate film (base material 1) except that the exemplified compound (2-3) is used instead of the exemplified compound (A-4). An acylate film (Substrate 2) was produced. Further, in the cellulose acylate film (base material 1), the cellulose acylate film (base material 3) was the same as the cellulose acylate film (base material 1) except that the exemplified compound (A-4) was not used. Manufactured.

<Preparation of antiglare layer>
The following anti-glare layer was provided on the cellulose acylate film (base materials 1 to 3).

(Synthesis of synthetic smectite)
10L beaker filled with water 4L of water glass No. 3 _{(SiO228%, Na 2 O9%} , molar ratio 3.22) was dissolved 860 g, a silicate solution is added in one portion with stirring of 95% sulfuric acid 162g Obtained. Next, 560 g of MgCl ₂ · 6H ₂ O primary reagent (purity 98%) was dissolved in 1 L of water, and this was added to the silicate solution to prepare a homogeneous mixed solution. This was dropped into 3.6 L of 2N-NaOH aqueous solution over 5 minutes with stirring. The reaction precipitate consisting of the obtained silicon-magnesium composite (a homogeneous composite in which colloidal particles are aggregated) is immediately filtered by a cross flow system (cross flow filter (ceramic) manufactured by NGK. Membrane filter: pore size 2 μm, tubular type, filtration area 400 cm ² )] and sufficiently washed with water, and then a slurry of 200 ml of water and 14.5 g of Li (OH) · H ₂ O was added to form a slurry. . This was transferred to an autoclave and subjected to a hydrothermal reaction at 41 kg / cm ² and 250 ° C. for 3 hours. After cooling, the reaction product was taken out, dried at 80 ° C., and pulverized to obtain a synthetic smectite having a composition of hectorite, which is one type of smectite, represented by the following formula.
Na _0.4 Mg _2.6 Li _0.4 Si ₄ O ₁₀ (OH) ₂

(Synthesis of smectite clay organic composite 1)
20 g of the synthetic smectite obtained above was dispersed in 1000 ml of tap water, and an article containing 80% of quaternary ammonium salt trioctyl methyl ammonium chloride was added to pure water in 11.1 g (trioctyl methyl ammonium chloride). As a result, 300 ml of dissolved product was added and reacted at room temperature (25 ° C.) for 2 hours with stirring. Next, the product was subjected to solid-liquid separation and washing to remove by-product salts, and then dried and pulverized to obtain a clay organic composite.

  When the obtained clay organic composite was measured by X-ray diffraction, the bottom face distance calculated from its (001) plane reflection was 18.0 mm, confirming the formation of a smectite clay organic composite. Dispersed in N, N-dimethylformamide to form a transparent dispersion. Further, the content of the quaternary ammonium salt was estimated from the analysis of the amount of nitrogen atoms by burning the clay organic composite, and it was 105 meq / 100 g smectite.

  In the above synthesis, the added amount of trioctyl / methyl / ammonium chloride is 110 meq / 100 g synthetic smectite, which means that 1.0 times the cation exchange capacity of the synthetic smectite is added.

(Preparation of coating solution for antiglare layer)
Each component was mixed with a mixed solvent of MIBK (methyl isobutyl ketone) and MEK (methyl ethyl ketone) so as to have a composition shown in Table 5 below. An antiglare layer coating solution was prepared by filtering through a polypropylene filter having a pore size of 30 μm. The solid content concentration of each coating solution is 35% by mass. In preparing the coating solution, the resin particles and the smectite clay organic composite were added in the form of a dispersion.

(Preparation of resin particle dispersion)
The dispersion of the translucent resin particles was prepared by gradually adding the translucent resin particles to the stirred MIBK solution until the solid content concentration of the dispersion reached 30% by mass and stirring for 30 minutes. The resin particles were cross-linked styrene-methyl made by Sekisui Plastics Co., Ltd., prepared by appropriately changing the copolymerization ratio of styrene and methyl methacrylate so that the average particle size was 2.5 μm and the refractive index was 1.52. Methacrylate copolymer particles were used.

(Preparation of smectite clay organic composite dispersion)
The dispersion of the smectite-type clay organic composite is finally added to all MEKs used in the coating solution for the antiglare layer, and the smectite-type clay organic composite is gradually added to the MEK while stirring and stirred for 30 minutes. Prepared.

The compounds used are shown below. Table 5 shows the content (% by mass) of each component with respect to the solid content of the coating solution for the antiglare layer (photocurable composition).
A-DPH: Dipentaerythritol hexaacrylate [manufactured by Shin-Nakamura Chemical Co., Ltd.]
Irgacure 907: Acetophenone photopolymerization initiator [manufactured by BASF] (referred to as “Irg907” in the table below)
Irgacure 184: Alkylphenone photopolymerization initiator [manufactured by BASF] (referred to as “Irg184” in the table below)
SP-13: The following fluorosurfactant (60:40 (molar ratio))
Addispar PB881: Dispersant [Ajinomoto Fine Techno Co., Ltd.]

(Coating of antiglare layer)
The cellulose acylate films (base materials 1 to 3) are unrolled in a roll form, and antiglare of Examples 1 to 17 and Comparative Examples 1 to 7 so as to have the film thickness shown in Table 5 below. Films 1 to 24 were produced.
Specifically, in the die coating method using the slot die described in JP-A-2006-122889, Example 1, each coating solution was applied under the condition of a conveyance speed of 30 m / min, and after drying at 80 ° C. for 150 seconds, Furthermore, using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) with an oxygen concentration of about 0.1% under a nitrogen purge, ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 180 mJ / cm ² were irradiated. After the coating layer was cured to form an antiglare layer, it was wound up.

<Preparation of polarizing plate>
Using the produced anti-glare films 1 to 24, a polarizing plate was produced as follows and the durability of the polarizing plate was evaluated.

(Saponification treatment of antiglare film)
The produced anti-glare film was immersed in a 2.3 mol / L aqueous sodium hydroxide solution at 55 ° C. for 3 minutes. It wash | cleaned in the room temperature water-washing bath, and neutralized using 0.05 mol / L sulfuric acid at 30 degreeC. Again, it was washed in a water bath at room temperature and further dried with hot air at 100 ° C. Thus, the surface saponification process was performed with respect to each anti-glare film.

(Preparation of polarizing plate)
A polarizer was produced by adsorbing iodine to a stretched polyvinyl alcohol film.
The saponified antiglare film 1 was attached to one side of a polarizer using a polyvinyl alcohol-based adhesive. A commercially available cellulose triacetate film (Fujitac TG60UL, manufactured by Fuji Film Co., Ltd.) is also subjected to the same saponification treatment, and the side opposite to the side on which the saponified antiglare film 1 is pasted using a polyvinyl alcohol adhesive. The commercially available cellulose triacetate film having been saponified was attached to the surface of the polarizer.
At this time, the polarizer was arranged so that the transmission axis of the polarizer and the slow axis of the saponified antiglare film 1 were parallel to each other. Further, the transmission axis of the polarizer and the slow axis of the commercially available cellulose triacetate film after saponification treatment were also arranged so as to be orthogonal to each other.
Thus, the polarizing plate 1 of the present invention was produced.

  For the antiglare films 2 to 17 and the antiglare films 18 to 24 of the comparative example, the saponification treatment and the preparation of the polarizing plate were respectively performed in the same manner as described above. ˜24 were prepared respectively.

<Evaluation of antiglare film and polarizing plate>
The following evaluation was performed with respect to the obtained anti-glare film and polarizing plate.

(Evaluation of polarizing plate durability)
The polarizing plate durability test was performed as follows in a form in which the polarizing plate was attached to glass through an adhesive.
Two samples (about 5 cm × 5 cm) in which a polarizing plate is attached on the glass so that the antiglare film of the present invention is on the air interface side are prepared. In the single plate orthogonal transmittance measurement, the antiglare film side of this sample is set facing the light source and measured. Two samples were measured respectively, and the average value was taken as the orthogonal transmittance of the polarizing plate. The orthogonal transmittance of the polarizing plate was measured in the range of 380 nm to 780 nm using an automatic polarizing film measuring device VAP-7070 manufactured by JASCO Corporation, and the measured value at 410 nm was adopted. Then, after storing for 240 hours in an environment of 80 ° C. and a relative humidity of 90% RH, the orthogonal transmittance was measured by the same method. The change of the orthogonal transmittance before and after aging was determined, and this was evaluated as the polarizing plate durability according to the following criteria.
In addition, the relative humidity in the environment without humidity control was in the range of 0 to 20% RH.
The obtained results are shown in Table 5 below.

A: Change in orthogonal transmittance before and after aging is less than 0.6% B: Change in orthogonal transmittance before and after aging is 0.6 to 1.0%
C: Change in orthogonal transmittance before and after aging exceeds 1.0% In the present invention, less than 1.0% was accepted (AB) and 1.0% or more was rejected (C).

  The obtained results are collectively shown in Table 5 described later.

(Glossiness evaluation)
The 20 ° glossiness of the produced antiglare film was measured according to JIS-Z8741 using a gloss meter (manufactured by Nippon Denka Kogyo Co., Ltd., VG2000). In the present invention, evaluation was performed according to the following criteria, and the evaluation results are shown in Table 5 below.
Glossiness in the range of 40 to 70: A
Glossiness of 30 to less than 40, or greater than 70 and less than or equal to 80: B
Glossiness less than 30 or greater than 80: C
In the present invention, 30 or more and 80 or less are acceptable (AB), less than 30 or larger than 80 are unacceptable (C).
The evaluation results are shown in Table 5 below.

(Pencil hardness)
The produced anti-glare film was evaluated by a pencil hardness test according to JIS K 5600-5-4 (1999). In the present invention, 2H or more is regarded as acceptable (A), and less than 2H is regarded as unacceptable (B).
The evaluation results are shown in Table 5 below.

  As can be seen from the results in Table 5, when the film thickness, resin particle content, and photopolymerization initiator content of the antiglare layer are within the range of the present invention, the polarizing plate durability, antiglare property, and hardness are extremely excellent. I understand.

DESCRIPTION OF SYMBOLS 1 Surface layer dope 2 Core layer (base layer) dope 3 Co-casting giusa 4 Casting support 21A, 21B Polarizing plate 22 Color filter substrate 23 Liquid crystal layer 24 Array substrate 25 Light guide plate 26 Light source 31a, 31b Anti-glare film ( Polarizing plate protective film)
32 Polarizer

Claims (7)

An antiglare film having an antiglare layer on a cellulose acylate film,
The cellulose acylate film contains a compound represented by the following general formula (1) and a sugar ester compound,
The antiglare layer has a thickness of 3.0 μm or more and 7.0 μm or less,
The antiglare layer is formed by curing a photocurable composition containing at least a) a curable compound, b) resin particles, and c) a photopolymerization initiator,
The content of the b) resin particles with respect to the solid content in the photocurable composition is 3% by mass or more and 10% by mass or less, and the content of the c) photopolymerization initiator is 1.5% by mass or more and 5% by mass. % Or less antiglare film.

R ¹³ represents an alkyl group, an alkenyl group or an aryl group, and R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heteroaryl group. R ¹¹ , R ¹² , and R ¹³ may each independently have a substituent. However, at least one of R ¹¹ , R ¹² , and R ¹³ includes an aromatic ring.   The antiglare film according to claim 1, wherein the antiglare layer has a thickness of 3.0 μm or more and 5.0 μm or less.   The antiglare film according to claim 1 or 2, wherein the content of the b) resin particles is 3% by mass or more and 8.5% by mass or less with respect to the solid content in the photocurable composition.   The content of said c) photoinitiator is 1.5 mass% or more and 3 mass% or less with respect to solid content in the said photocurable composition, Prevention of any one of Claims 1-3 Dazzle film. The antiglare film according to any one of claims 1 to 4, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2-a).

L ^{1 to} L ³ each independently represents a single bond or an alkylene group. Ar ^{1 to} Ar ³ each independently represents an aryl group having 6 to 20 carbon atoms.   A polarizing plate having at least the antiglare film according to any one of claims 1 to 5 and a polarizer.   A liquid crystal display device comprising at least the polarizing plate according to claim 6 and a liquid crystal cell.

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